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EP3329509A1 - Procédés de croissance de nanofils ou de nanopyramides sur des substrats graphitiques - Google Patents

Procédés de croissance de nanofils ou de nanopyramides sur des substrats graphitiques

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Publication number
EP3329509A1
EP3329509A1 EP16754215.8A EP16754215A EP3329509A1 EP 3329509 A1 EP3329509 A1 EP 3329509A1 EP 16754215 A EP16754215 A EP 16754215A EP 3329509 A1 EP3329509 A1 EP 3329509A1
Authority
EP
European Patent Office
Prior art keywords
nanowires
nanopyramids
layer
substrate
graphitic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP16754215.8A
Other languages
German (de)
English (en)
Inventor
Dong-Chul Kim
Ida Marie HØIAAS
Mazid MUNSHI
Bjørn Ove FIMLAND
Helge Weman
Dingding REN
Dasa DHEERAJ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Norwegian University of Science and Technology NTNU
Crayonano AS
Original Assignee
Norwegian University of Science and Technology NTNU
Crayonano AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB1513567.6A external-priority patent/GB201513567D0/en
Priority claimed from GBGB1600162.0A external-priority patent/GB201600162D0/en
Application filed by Norwegian University of Science and Technology NTNU, Crayonano AS filed Critical Norwegian University of Science and Technology NTNU
Priority to EP19173937.4A priority Critical patent/EP3544046A1/fr
Publication of EP3329509A1 publication Critical patent/EP3329509A1/fr
Pending legal-status Critical Current

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    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02376—Carbon, e.g. diamond-like carbon
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/0242—Crystalline insulating materials
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    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02441—Group 14 semiconducting materials
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02455—Group 13/15 materials
    • H01L21/02458—Nitrides
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    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
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    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
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    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02579—P-type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells

Definitions

  • This invention concerns the use of a thin graphitic layer as a transparent, conductive and flexible substrate for nanowire or nanopyramid arrays preferably grown by a bottom-up method using metal-organic vapour phase epitaxy (MOVPE) or molecular beam epitaxy (MBE).
  • MOVPE metal-organic vapour phase epitaxy
  • MBE molecular beam epitaxy
  • Nanowires which are also referred to as nanowhiskers, nanorods, nanopillars, nanocolumns, etc. by some authors, have found important applications in a variety of electrical and optoelectrical devices such as sensors, solar cells to LEDs.
  • nanowire is to be interpreted as a structure being essentially in one-dimensional form, i.e. is of nanometer
  • nanowires are considered to have at least two dimensions not greater than 500 nm, such as not greater than 350 nm, especially not greater than 300 nm such as not greater than 200 nm.
  • nanowires include metallic (e.g., Ni, Pt, Au), semiconducting (e.g., Si, InP, GaN, GaAs, ZnO), and insulating (e.g., Si0 2 , Ti0 2 ) nanowires.
  • metallic e.g., Ni, Pt, Au
  • semiconducting e.g., Si, InP, GaN, GaAs, ZnO
  • insulating e.g., Si0 2 , Ti0 2
  • GaAs nanowires are grown on GaAs substrates and so on. This, of course, ensures that there is a lattice match between the crystal structure of the substrate and the crystal structure of the growing nanowire. Both substrate and nanowire can have identical crystal structures.
  • the present invention concerns nanowires grown on graphitic substrates.
  • Graphitic substrates are substrates composed of single or multiple layers of graphene or its derivatives. In its finest form, graphene is a one atomic layer thick sheet of carbon atoms bound together with double electron bonds (called a sp 2 bond) arranged in a honeycomb lattice pattern. Graphitic substrates are thin, light, and flexible, yet very strong.
  • WO2012/080252 there is a discussion of the growth of semiconducting nanowires on graphene substrates using molecular beam epitaxy.
  • WO2013/ 104723 concerns improvements on the '252 disclosure in which a graphene top contact is employed on nanowires grown on graphene.
  • nanowires can be grown perpendicular to the substrate surface.
  • Semiconductor nanowires normally grow in the [111] direction (if cubic crystal structure) or the [0001] direction (if hexagonal crystal structure). This means that the substrate surface needs to be (111) or (0001) oriented where the surface atoms of the substrate is arranged in a hexagonal symmetry.
  • the present invention relates, inter alia, to functionalization of the graphene surface or to the inclusion of new layers or small islands on top of the graphene surface to enhance nucleation of nanowires thereon.
  • the inventors still benefit, however, from the remarkable properties of graphene in terms of its strength, flexibility, transparency and electrical conductivity.
  • the invention provides a process for growing nanowires or nanopyramids comprising:
  • the invention provides a process for growing nanowires or nanopyramids comprising:
  • the invention provides a process for growing nanowires or nanopyramids comprising:
  • the at least one group V species is not N.
  • the invention provides a process for growing nanowires or nanopyramids comprising: (I) providing a graphitic substrate and depositing on said graphitic substrate Al to form an Al layer or nanoscale Al islands;
  • the group V element may be in the form of a monomer, dimer, trimer or tetramer of the element such as As 2 and Sb 2 .
  • the invention provides a process for growing nanowires or nanopyramids comprising:
  • step (II) annealing the treated substrate of step (I) in the presence of hydrogen to convert at least a portion of said C-0 bonds to C-H bonds;
  • step (III) growing a plurality of semiconducting group III-V nanowires or nanopyramids on the annealed surface of step (II), preferably via MOVPE or MBE.
  • the invention provides a process for growing nanowires or nanopyramids comprising:
  • the invention provides a product obtained by process as hereinbefore defined.
  • the invention provides a device, such as an electronic device, comprising a product as hereinbefore defined, e.g. a solar cell, light emitting device or photodetector.
  • a product as hereinbefore defined, e.g. a solar cell, light emitting device or photodetector.
  • a group III-V compound semiconductor is meant one comprising at least one element from group III and at least one element from group V. There may be more than one element present from each group, e.g. InGaAs, AlGaN (i.e. a ternary compound), AlInGaN (i.e. a quaternary compound) and so on.
  • InGaAs InGaAs, AlGaN (i.e. a ternary compound), AlInGaN (i.e. a quaternary compound) and so on.
  • nanowire or nanopyramid is meant nanowire or nanopyramid made of semiconducting materials from group III-V elements.
  • Nanowire is used herein to describe a solid, wire-like structure of nanometer dimensions. Nanowires preferably have an even diameter throughout the majority of the nanowire, e.g. at least 75% of its length.
  • the term nanowire is intended to cover the use of nanorods, nanopillars, nanocolumns or nanowhiskers some of which may have tapered end structures.
  • the nanowires can be said to be in essentially in one-dimensional form with nanometer dimensions in their width or diameter and their length typically in the range of a few 100 nm to a few ⁇ .
  • the nanowire diameter is not greater than 500 nm. Ideally, the nanowire diameter is between 50 and 500 nm, however, the diameter can exceed few microns (called micro wires).
  • the diameter at the base of the nanowire and at the top of the nanowire should remain about the same (e.g. within 20% of each other).
  • the substrate carries a plurality of nanowires. This may be called an array of nanowires.
  • nanopyramid refers to a solid pyramidal type structure.
  • pyramidal is used herein to define a structure with a base whose sides taper to (almost) a single point generally above the centre of the base. It will be appreciated that the single vertex point may appear chamferred.
  • the nanopyramids may have multiple faces, such as 3 to 8 faces, or 4 to 7 faces.
  • nanopyramids might be a square, pentagonal, hexagonal, heptagonal, octagonal and so on.
  • the pyramid is formed as the faces taper from the base to a central point (forming therefore triangular faces).
  • the base itself may comprise a portion of even cross-section before tapering to form a pyramidal structure begins.
  • the thickness of the base may therefore be up to 200 nm, such as 50 nm.
  • the base of the nanopyramids can be 50 and 500 nm in diameter across its widest point.
  • the height of the nanopyramids may be 500 nm to a few microns.
  • the substrate carries a plurality of nano wires or nanopyramids. This may be called an array of nanowires or nanopyramids.
  • Graphitic layers for substrates or possibly for top contacts are films composed of single or multiple layers of graphene or its derivatives.
  • the term graphene refers to a planar sheet of sp 2 -bonded carbon atoms in a honeycomb crystal structure.
  • epitaxy comes from the Greek roots epi, meaning “above”, and taxis, meaning “in ordered manner”.
  • the atomic arrangement of the nanowire or nanopyramid is based on the crystallographic structure of the substrate. It is a term well used in this art.
  • Epitaxial growth means herein the growth on the substrate of a nanowire or nanopyramid that mimics the orientation of the substrate or mimics the orientation of the Si layer, buffer layer or nucleation islands, depending on the embodiment in question.
  • MBE is a method of forming depositions on crystalline substrates.
  • the MBE process is performed by heating a crystalline substrate in a vacuum so as to energize the substrate's lattice structure. Then, an atomic or molecular mass beam(s) is directed onto the substrate's surface.
  • the term element used above is intended to cover application of atoms, molecules or ions of that element.
  • the directed atoms or molecules arrive at the substrate's surface, the directed atoms or molecules encounter the substrate's energized lattice structure or a catalyst droplet as described in detail below. Over time, the oncoming atoms form a nanowire.
  • MOVPE also called as metal organic chemical vapour deposition (MOCVD) is an alternative method to MBE for forming depositions on crystalline substrates.
  • MOCVD metal organic chemical vapour deposition
  • the deposition material is supplied in the form of metal organic precursors, which on reaching the high temperature substrate decompose leaving atoms on the substrate surface.
  • this method requires a carrier gas (typically H 2 and/or N 2 ) to transport deposition materials (atoms/molecules) across the substrate surface. These atoms reacting with other atoms form an epitaxial layer on the substrate surface. Choosing the deposition parameters carefully results in the formation of a nanowire.
  • MIC metal-induced crystallization
  • This invention concerns the use of graphitic layers as a substrate for nanowire or nanopyramid growth or as a substrate for carrying a further layer on which nanowires or nanopyramids will grow.
  • the graphitic layer is transparent, conductive and flexible.
  • the semiconductor nanowire or nanopyramid array comprises a plurality of nanowires or nanopyramids preferably grown epitaxially from said graphitic substrate or from the top layer present.
  • nanowire or nanopyramid grown epitaxially provides homogeneity to the formed material which may enhance various end properties, e.g. mechanical, optical or electrical properties.
  • Epitaxial nanowires or nanopyramids may be grown from gaseous, liquid or solid precursors. Because the substrate acts as a seed crystal, the deposited nanowire or nanopyramid can take on a lattice structure and orientation identical to those of the substrate. This is different from other thin film deposition methods which deposit polycrystalline or amorphous films, even on single-crystal substrates. Substrate for nanowire or nanopyramid growth
  • the substrate used to grow nanowires or nanopyramids is a graphitic substrate, more especially it is graphene.
  • graphene refers to a planar sheet of sp 2 -bonded carbon atoms that are densely packed in a honeycomb (hexagonal) crystal lattice.
  • This graphene substrate should preferably be no more than 20 nm in thickness. Ideally, it should contain no more than 10 layers of graphene or its derivatives, preferably no more than 5 layers (which is called as a few-layered graphene). Especially preferably, it is a one-atom-thick planar sheet of graphene.
  • the crystalline or "flake” form of graphite consists of many graphene sheets stacked together (i.e. more than 10 sheets).
  • graphitic substrate therefore, is meant one formed from one or a plurality of graphene sheets.
  • the substrate in general is 20 nm in thickness or less.
  • Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm.
  • the graphitic substrate preferred comprises only a few such layers and may ideally be less than 10 nm in thickness. Even more preferably, the graphitic substrate may be 5 nm or less in thickness.
  • the area of the substrate in general is not limited. This might be as much as 0.5 mm 2 or more, e.g. up to 5 mm 2 or more such as up to 10 cm 2 . The area of the substrate is thus only limited by practicalities.
  • the substrate is a laminated substrate exfoliated from a Kish graphite, a single crystal of graphite or is a highly ordered pyrolytic graphite (HOPG).
  • the substrate could be grown on a Ni film or Cu foil by using a chemical vapour deposition (CVD) method.
  • the substrate could be a chemical vapour deposition (CVD)-grown graphene substrate on metallic films or foils made of e.g. Cu, Ni, or Pt, and on semiconductors such as Si and Ge, and on insulators such as Si0 2 and A1 2 0 3 .
  • High quality graphene grown on SiC film by Si sublimation at high temperature could be also used.
  • These grown graphitic layers can be exfoliated from the growth substrate and transferred.
  • CVD-grown graphitic layers can be chemically exfoliated from the metal foil such as a Ni or Cu film by etching or by an electrochemical de lamination method.
  • the graphitic layers after exfoliation are then transferred and deposited to the supporting substrates for nanowire or nanopyramid growth.
  • e-beam resist or photoresist may be used to support the thin graphene layers. These supporting materials can be easily removed by acetone after deposition.
  • a thin buffer layer or nanoscale nucleation islands could be grown on the graphitic surface.
  • the buffer layer could be made of A1N or AlGaN or AlGaInN or InGaN, which enhances the density, and controls the polarity and orientation of nanowires or nanopyramids such as GaN.
  • A1N buffer layer has been previously reported for GaN nanowire or nanopyramid growth on Si substrates (Nanotechnology 26 (2015) 085605); however, not on graphitic substrates.
  • the buffer layer on the graphitic substrate can be grown by migration enhanced epitaxy (MEE). Tuning the growth conditions, such as temperature and V/III ratio, and the thickness of the buffer layer, the density, alignment and polarity of the nanowires or nanopyramids can be controlled.
  • MEE migration enhanced epitaxy
  • nanoscale nucleation islands of A1N or AlGaN or AlGaInN or InGaN on graphitic substrate can be used to facilitate the growth of nanowires or nanopyramids.
  • These nucleation islands increase the density, and control the polarity and alignment of nanowires or nanopyramids.
  • AlGaN islands can be grown on a graphitic substrate. The density of the islands can be increased by increasing the island growth time. Then the nanowire or nanopyramid growth (e.g. GaN or AlGaN) can be initiated on the said islands.
  • nucleation islands as compared to a buffer layer has some additional advantages.
  • the graphitic surface does not get covered by the buffer layer that might reduce the transparency of graphene.
  • the nucleation island size typically 5-20 nm
  • the nanowire or nanopyramid diameter typically 50-500 nm
  • the electrical conduction path between nanowire or nanopyramid and graphene is not much compromised; especially, with regard to the case when the buffer layer is undoped or has a higher bandgap (e.g. A1N and AlGaN) than the nanowire or nanopyramid (e.g. GaN and InGaN).
  • the graphitic surface before nanowire or nanopyramid growth the graphitic surface is subjected to a nitrogen plasma, leading to the incorporation of nitrogen as a substitutional impurity or/and formation of ledges and step edges on its surface, preferably both.
  • the atomic ledges facilitate the nucleation of nanowires or nanopyramids as mentioned above.
  • the inclusion of nitrogen changes the Fermi level and hence the electronic structure of the graphitic substrate (Nano Lett. 8, 4373, (2008)).
  • the inclusion of nitrogen also increases the chemical reactivity of the graphitic substrate and makes nanowire or nanopyramid nucleation on the surface easier.
  • doping such as n-type doping of the graphene in combination with nitrogen plasma may facilitate nanowire or nanopyramid growth and further device fabrication.
  • the invention relates to the introduction of a buffer layer or nanoscale islands of an Al-group V compound such as AlAs, AlAsSb or AlSb on the graphitic substrate.
  • Al is first deposited on the graphitic substrate to form a thin Al layer or nanoscale Al islands on the graphitic substrate. Due to the relatively high binding energy and thus a low diffusion coefficient of the Al adatoms, Al tends to stick on the graphitic surface.
  • Group V element flux such as As and/or Sb fluxes are provided onto the above Al layer or nanoscale islands, thereby forming a buffer layer or nanoscale islands of Al-group V compound such as AlAs, AlAsSb or AlSb.
  • a change in the surface energy by the introduction of the buffer layer or nanoscale islands facilitates the nucleation and growth of nanowires or nanopyramids.
  • the flux may be in the form of monomers, dimers, trimers or tetramers, such as As 2 and Sb 2 .
  • an Al layer of nominal thickness 0.01 to 2 nm is deposited on the graphitic substrate such as at temperatures between 500-700 °C.
  • the layer is then transformed into a buffer layer or nanoscale islands of AlAs, AlAsSb or AlSb by supplying As and/or Sb fluxes such as in the range of 0.05-5 x 10 "6 Torr, such as l-3 l0 "6 Torr.
  • Ga droplets are formed on the said buffer layer or nanoscale islands by supplying only Ga flux to catalyse the growth of a plurality of semiconducting group III-V nanowires, preferably nanowires comprising GaAs and/or GaAsSb, on said buffer layer or nucleation islands on the graphitic substrate, preferably via MOVPE or MBE. Nanowires preferably grow perpendicular to the substrate.
  • defects and holes of single or multiple atomic layers in depth are formed on the graphitic substrate.
  • defects or holes steps or ledges are formed on the graphitic substrate.
  • steps or ledges are created on the graphitic substrate that aid the nucleation of nanowires or nanopyramids.
  • This can be achieved through treatment with oxygen plasma or through treatment with ozone, e.g. UV and ozone.
  • the treatment is preferably effected at elevated temperature, such as 100°C or more, ideally 125 to 175°C, such as 150°C.
  • the etching process appears to work better at these slightly elevated temperatures.
  • the use of elevated temperatures begins the annealing process described below.
  • this treatment introduces oxygen atoms to the surface of the graphitic layer, typically via the formation of an epoxide group on the graphitic surface.
  • the treatment introduces both ledges/steps and oxygen atoms to the surface of the graphitic layer.
  • the use of elevated temperatures during the treatment process may also enhance the etching process (i.e. the formation of ledges).
  • this surface treatment results in the formation of a rough graphitic surface, with holes and defects on the surface of the graphitic substrate, and the carbon dangling bonds are bonded with oxygen atoms.
  • the introduction of ledges onto the substrate surface increases the surface roughness and creates a fluctuation in surface potential of the substrate making nucleation thereon easier.
  • the surface of the UV-ozone or oxygen plasma treated graphitic substrate could itself be used as a surface for nanowire or nanopyramid nucleation; however, the inventors have found that annealing the treated graphitic substrate with hydrogen results in a more interesting surface for nanowire or nanopyramid nucleation.
  • the ozone or oxygen plasma treated graphitic substrate is annealed in the presence of hydrogen, typically in an inert atmosphere.
  • the annealing process may take place at a temperature of 100 to 500 C, such as 250 to 400 °C.
  • a suitable graphene treatment process is described in Science 330 (2010) 655.
  • the inert gas is typically nitrogen or a noble gas such as argon.
  • the annealing process reduces the epoxide surface groups at the ledges down to C-H groups and therefore provides an improved surface for nanowire or nanopyramid nucleation and hence nanowire or nanopyramid growth.
  • the C-H bond is believed to break at the elevated temperatures used for nanowire or nanopyramid growth, leaving the surface with dangling bond for the nanowire or nanopyramid nucleation to take place. Also, it is believed that the oxygen or ozone treatment causes vertical etching of the graphitic substrate and hence the
  • the annealing process causes lateral etching increasing surface roughness across the surface of the substrate.
  • the invention relates to the introduction of a crystalline Si layer, in particular an alpha-crystalline Si(l 11) layer onto the graphitic substrate using the metal-induced crystallization (MIC) process.
  • a crystalline Si layer in particular an alpha-crystalline Si(l 11) layer onto the graphitic substrate using the metal-induced crystallization (MIC) process.
  • MIC metal-induced crystallization
  • Al layer can be deposited by any known technique such as e- beam or thermal evaporation, atomic layer deposition (ALD), CVD and so on.
  • the inventors have shown that the electron beam evaporation of Al can be used, something which ensures that the graphitic surface is not damaged in said process.
  • the graphitic surface is modified only at those spots where nanowires are to nucleate, whereas the rest of the graphitic surface should remain undamaged in order to keep the good electrical properties of the graphitic surface between the nanowires or nanopyramids.
  • the Al layer is preferably 10 to 30 nm in thickness.
  • the uppermost atomic layers of this Al layer are preferably oxidised by exposing the Al to an oxygen source such as air.
  • the uppermost atomic layers are preferably represented by around the top 5 nm of the Al layer.
  • a Si layer is applied on top of the oxidised Al layer (aluminium oxide layer). Again, the same application techniques can be employed.
  • the Si layer is amorphous at this point.
  • a structure is preferably formed in which a graphitic substrate carries an Al layer, an oxidised Al layer and an amorphous Si layer, in that order.
  • the Si layer can be 5 to 50 nm in thickness
  • Annealing may take place at a temperature of 300 to 500 °C. Typically, annealing occurs in an inert atmosphere, such as an atmosphere of nitrogen.
  • the as-deposited Al layer on arbitrary substrates is polycrystalline with no preferential orientation of the grains.
  • the Si layer is also amorphous at this stage with no crystalline Si before annealing. Therefore, the initial bilayer consists of amorphous Si on top of polycrystalline Al, with a thin oxide interface.
  • Si atoms diffuse into the Al layer and form spontaneously crystalline nuclei.
  • the driving force is the free energy difference between the amorphous and crystalline phases of Si.
  • the Al and Si layers have exchanged their initial stacking position: the Al layer is on top of the stack.
  • a (Si)Al-oxide layer is located between the Al and Si layers at this point.
  • the crystallization of Si grains is
  • the present inventors have found that the electron beam evaporation of Al on graphene can give a preferable (11 l)-orientation of the Al layer, which is much enhanced compared to that on amorphous Si0 2 substrates. This subsequently results in a highly (1 1 l)-oriented Si film on graphene after the AIC process without any damage in the graphene substrate.
  • the Al layer can then be removed, preferably via etching of the Al layer (as well as any (Si)Al-oxide in-between the two layers) to leave a substrate coated with a mainly (11 1) crystalline nanostructured Si layer on the graphitic substrate.
  • the Si layer at this point can be 5 to 50 nm in thickness. Since the Si layer is very thin, the properties of underlying graphene can still be realised, i.e. it will still be flexible, conductive and mostly transparent.
  • a further advantage of using the Si layer is that the nanowire or nanopyramid growth recipe can readily be transferred from the growth on standard Si(l 11) substrates.
  • nanowire or nanopyramid growth takes place on the Si layer on top of graphic substrate, the standard recipes for growing III-V nanowires or nanopyramids on Si can readily be applied. Moreover, the density of nanowires or nanopyramids is much higher than on the bare graphitic substrate. In addition one can grow nanowires or nanopyramids at a higher temperature which is generally used for the nanowire or nanopyramid growth on Si(l 11) instead of the two step growth of nanowires or nanopyramids on graphitic substrates involving a low-temperature step, which is the cause for the two- dimensional growth of (unwanted) parasitic III-V semiconductor materials. This would decrease the parasitic crystal growth of III-V semiconductor materials on the substrate. Combining with a mask with hole pattern on top of the Si(l 11) layer, one can achieve the nanowire or nanopyramid growth only at exposed hole region by high temperature growth, resulting in a positon-controlled or selective area growth.
  • the graphitic substrate may need to be supported in order to allow growth of the nanowires or nanopyramids thereon.
  • the substrate can be supported on any kind of material including conventional semiconductor substrates and transparent glasses. It is preferred if the support is transparent so that the substrate does not block light from exiting or entering the device.
  • Examples of preferred substrates include fused silica, fused quartz, fused alumina, silicon carbide or A1N.
  • the use of fused silica or SiC is preferred, especially fused silica.
  • the support should be inert. After nanowire or
  • Nanopyramid growth and before use in a device, the support might be removed, e.g. by peeling away the support from the graphitic substrate.
  • nanowires or nanopyramids of commercial importance, it is preferred that these grow epitaxially on the substrate, Si layer, buffer layer or nucleation islands. It is also ideal if growth occurs perpendicular to the growing surface and ideally therefore in the [11 1] (for cubic crystal structure) or [0001] (for hexagonal crystal structure) direction.
  • the present inventors have determined that epitaxial growth on graphitic substrates is possible by determining a possible lattice match between the atoms in the semiconductor nanowire or nanopyramid and the carbon atoms in the graphene sheet.
  • the carbon-carbon bond length in graphene layers is about 0.142 nm.
  • Graphite has hexagonal crystal geometry.
  • the present inventors have previously realised that graphite can provide a substrate on which semiconductor nanowires or nanopyramids can be grown as the lattice mismatch between the growing nanowire or nanopyramid material and the graphitic substrate can be very low.
  • the inventors have realised that due to the hexagonal symmetry of the graphitic substrate and the hexagonal symmetry of the semiconductor atoms in the (111) planes of a nanowire or nanopyramid growing in the [111] direction with a cubic crystal structure (or in the (0001) planes of a nanowire or nanopyramid growing in the [0001] direction with a hexagonal crystal structure), a lattice match can be achieved between the growing nanowires or nanopyramids and the substrate.
  • nanopyramids of such materials to be vertically grown to form free standing nanowires or nanopyramids on top of a thin carbon-based graphitic material.
  • the triangular side surfaces with (1-101) facets could either converge to a single point at the tip or could form a new facets ((1-102) planes) before converging at the tip.
  • the nanopyramids are truncated with its top terminated with ⁇ 0001 ⁇ planes.
  • nanowires or nanopyramids Whilst it is ideal that there is no lattice mismatch between a growing nanowire or nanopyramid and the substrate, nanowires or nanopyramids can accommodate much more lattice mismatch than thin films for example.
  • the nanowires or nanopyramids of the invention may have a lattice mismatch of up to about 10% with the substrate and epitaxial growth is still possible. Ideally, lattice mismatches should be 7.5% or less, e.g. 5% or less.
  • the nanowire or nanopyramid grown in the present invention may be from 250 nm to several microns in length, e.g. up to 5 microns. Preferably the nanowires or nanopyramids are at least 1 micron in length. Where a plurality of nanowires or nanopyramids are grown, it is preferred if they all meet these dimension
  • At least 90% of the nanowires grown will be at least 1 micron in length. Preferably substantially all the nanowires will be at least 1 micron in length.
  • Nanowires/nanopyramids can be controlled through flux ratios. Nanopyramids are encouraged, for example if high group V flux is employed. Moreover, it will be preferred if the nanowires grown have the same dimensions, e.g. to within 10% of each other. Thus, at least 90% (preferably substantially all) of the nanowires will preferably be of the same diameter and/or the same length (i.e. to within 10% of the diameter/length of each other). Essentially, therefore the skilled man is looking for homogeneity and nanowires then are substantially the same in terms of dimensions.
  • the length of the nanowires or nanopyramids is often controlled by the length of time for which the growing process runs. A longer process typically leads to a (much) longer nanowire.
  • the nanowires or nanopyramids have typically a hexagonal cross sectional shape.
  • the nanowire or nanopyramid may have a cross sectional diameter of 25 to 200 nm (i.e. its thickness). As noted above, the diameter is ideally constant throughout the majority of the nanowire. Nanowire diameter can be controlled by the manipulation of the ratio of the atoms used to make the nanowire as described further below.
  • the length and diameter of the nanowires or nanopyramids can be affected by the temperature at which they are formed. Higher temperatures encourage high aspect ratios (i.e. longer and/or thinner nanowires). The skilled man is able to manipulate the growing process to design nanowires of desired dimensions.
  • the nanowires or nanopyramids of the invention are formed from at least one III-V compound.
  • Group III options are B, Al, Ga, In, and Tl.
  • Preferred options here are Ga, Al and In.
  • Group V options are N, P, As, Sb. All are preferred.
  • Preferred compounds for nanowire or nanopyramid manufacture include AlAs, GaSb, GaP, GaN, AIN, AlGaN, AlGalnN, GaAs, InP, InN, InGaAs, InSb, InAs, or AlGaAs.
  • Compounds based on Al, Ga and In in combination with N are one option.
  • the use of GaN, AlGaN, AUnGaN or AIN is highly preferred, especially in combination with a group III-N buffer layer or nucleation islands.
  • there are two group III cations with a group V anion are preferred, such as AlGaN.
  • the ternary compounds may therefore be of formula XYZ wherein X is a group III element, Y is a group III different from X, and Z is a group V element.
  • the X to Y molar ratio in XYZ is preferably 0.1 to 0.9, i.e. the formula is preferably X x Yi_ x Z where subscript x is 0.1 to 0.9.
  • Quaternary systems might also be used and may be represented by the formula A x Bi_ x C y Di_ y where A and B are group III elements and C and D are group V elements. Again subscripts x and y are typically 0.1 to 0.9. Other options will be clear to the skilled man.
  • the nanowires or nanopyramids of the invention should preferably grow in the [111] direction for nanowires or nanopyramids with cubic crystal structure and [0001] direction for nanowires or nanopyramids with hexagonal crystal structure. If the crystal structure of the growing nanowire or nanopyramid is cubic, then the (111) interface between the nanowire or nanopyramid and the catalyst droplet represents the plane from which axial growth takes place. If the nanowire or nanopyramid has a hexagonal crystal structure, then the (0001) interface between the nanowire or nanopyramid and the catalyst droplet represents the plane from which axial growth takes place. Planes (111) and (0001) both represent the same
  • the nanowires or nanopyramids are preferably grown by MBE or MOVPE.
  • the growing surface is provided with a molecular beam of each reactant, e.g. a group III element and a group V element preferably supplied simultaneously.
  • a higher degree of control of the nucleation and growth of the nanowires or nanopyramids on the graphitic substrate might be achieved with the MBE technique by using migration-enhanced epitaxy (MEE) or atomic-layer MBE (ALMBE) where e.g. the group III and V elements can be supplied alternatively.
  • MEE migration-enhanced epitaxy
  • AMBE atomic-layer MBE
  • a preferred technique is solid-source MBE, in which very pure elements such as gallium and arsenic are heated in separate effusion cells, until they begin to slowly evaporate (e.g. gallium) or sublimate (e.g. arsenic).
  • a rf-plasma nitrogen source is typically used to produce low energy beams of nitrogen atoms.
  • the gaseous elements then condense on the substrate, where they may react with each other.
  • single-crystal GaAs is formed.
  • beam implies that evaporated atoms (e.g. gallium) or molecules (e.g. As 4 or As 2 ) do not interact with each other or vacuum chamber gases until they reach the substrate.
  • MBE takes place in ultra-high vacuum, with a background pressure of typically around 10 ⁇ 10 to 10 ⁇ 9 Torr.
  • Nanostructures are typically grown slowly, such as at a speed of up to a few, such as about 10, im per hour. This allows nanowires or nanopyramids to grow epitaxially and maximises structural performance.
  • the substrate is kept in a reactor in which the substrate is provided with a carrier gas and a metal organic gas of each reactant, e.g. a metal organic precursor containing a group III element and a metal organic precursor containing a group V element.
  • the typical carrier gases are hydrogen, nitrogen, or a mixture of the two.
  • the nanowires or nanopyramids of the invention may be grown with or without the presence of a catalyst.
  • Catalyst can be introduced to provide nucleating sites for nanowire or nanopyramid growth.
  • the catalyst can be one of the elements making up the nanowire or nanopyramid - so called self-catalysed, or different from any of the elements making up the nanowire.
  • the catalyst may be Au or Ag or the catalyst may be a metal from the group used in the nanowire or nanopyramid growth (e.g. group III metal), especially one of the metal elements making up the actual nanowire or nanopyramid (self-catalysis). It is thus possible to use another element from group III as a catalyst for growing a III-V nanowire, e.g. use Ga as a catalyst for an In-V) nanowire or nanopyramid and so on.
  • the catalyst is Au or the growth is self-catalysed (i.e. Ga for a Ga- V) nanowire or nanopyramid and so on).
  • the catalyst can be deposited onto the growing surface to act as a nucleation site for the growth of the nanowires or nanopyramids. Ideally, this can be achieved by providing a thin film of catalytic material formed over the growing surface. When the catalyst film is melted as the temperature increases to the nanowire or nanopyramid growth temperature, the catalyst forms nanometre sized particle-like droplets on the growing surface and these droplets form the points where nanowires or nanopyramids can grow.
  • VLS vapour- liquid- so lid growth
  • the molecular beam is the vapour
  • the nanowire or nanopyramid provides the solid component.
  • the catalyst particle can also be solid during the nanowire or nanopyramid growth, by a so called vapour- so lid- so lid growth (VSS) mechanism.
  • VLS vapour- so lid- so lid growth
  • the liquid e.g. gold
  • a mask can be used on the substrate.
  • This mask can be provided with regular holes, where catalyst particles (of one of the group-Ill elements) are deposited in the holes such that nanowires or nanopyramids can grow homogeneously in size in a regular array across the substrate.
  • the hole patterns in the mask can be easily fabricated using conventional photo/e-beam lithography or nanoimprinting. Focussed ion beam technology may also be used in order to create a regular array of nucleation sites on the graphitic surface for the nanowire or nanopyramid growth.
  • a thin film of Au such as with a thickness less than 50 nm, can be deposited on a hole-patterned photo or e-beam resist.
  • a regular arrayed pattern of Au dots on the substrate surface can be fabricated.
  • the growth of nanowires or nanopyramids without the presence of a catalyst is also possible and is known as selective area growth method.
  • This method may require a mask with nano-hole patterns deposited on the graphitic layers as described herein.
  • the mask material can be an oxide or nitride masking layer, preferably a metal oxide or metal nitride layer or semimetal oxide or semimetal nitride).
  • the mask layer can be applied through atomic layer deposition or the techniques discussed above in connection with the deposition of the other layers.
  • the oxide used is preferably based on a metal or semimetal (such as Si).
  • the nature of the cation used in the masking layer may be Al, Si or a transition metal, especially a first 3d row transition metal (Sc-Zn).
  • Preferred masking layers are based on oxides, such as SiC"2, S13N4, T1O2 or AI2O3, W2O3, and so on.
  • Masking layers may be 5 to 100 nm in thickness, such as 10 to 50 nm.
  • the masking layer is preferably continuous and covers the substrate as a whole. This ensures that the layer is defect-free and thus prevents nucleation of nanowires or nanopyramids on the masking layer.
  • a mask can be applied to the substrate and etched with holes exposing the substrate surface, optionally in a regular pattern. Moreover, the size and the pitch of the holes can be carefully controlled. By arranging the holes regularly, a regular pattern of nanowires or nanopyramids can be grown.
  • the size of the holes can be controlled to ensure that only one nanowire or nanopyramid can grow in each hole.
  • the holes can be made of a size where the hole is sufficiently large to allow nanowire or nanopyramid growth. In this way, a regular array of nanowires can be grown.
  • the graphitic surfaces may be treated with the above mentioned techniques (oxygen or ozone treatment and hydrogenation, nitrogen plasma, MIC of amorphous silicon, deposition of buffer layer, or formation of nucleation islands) before or after the deposition of mask.
  • self-catalysed nanowires As noted above, it is also possible to prepare self-catalysed nanowires.
  • self-catalysed is meant that one of the components of the nanowire or nanopyramid acts as a catalyst for its growth.
  • a Ga layer can be applied to the hole-patterned mask layer, melted to form droplets acting as nucleation sites for the growth of Ga containing nanowires.
  • a Ga metal portion may end up positioned on the top of the nanowire.
  • a Ga/In flux can be supplied to the substrate surface for a period of time to initiate the formation of Ga/In droplets on the surface upon heating of the substrate.
  • the substrate temperature can then be set to a temperature suitable for the growth of the nanowire or nanopyramid in question.
  • the growth temperature may be in the range 300 to 700°C.
  • the temperature employed is, however, specific to the nature of the material in the nanowire, the catalyst material and the substrate material.
  • a preferred temperature is 540 to 630°C, e.g. 590 to 630 °C, such as 610°C.
  • InAs the range is lower, for example 420 to 540°C, such as 430 to 540°C, e.g. 450°C.
  • Nanowire or nanopyramid growth can be initiated by opening the shutter of the Ga/In effusion cell and the counter ion effusion cell, simultaneously once a catalyst film has been deposited and melted.
  • the temperature of the effusion cells can be used to control growth rate.
  • Convenient growth rates as measured during conventional planar (layer by layer) growth, are 0.05 to 2 ⁇ ⁇ hour, e.g. 0.1 ⁇ ⁇ hour.
  • the pressure of the molecular beams can also be adjusted depending on the nature of the nanowire or nanopyramid being grown. Suitable levels for beam equivalent pressures are between 1 x 10 "7 and 1 x 10 "5 Torr.
  • the beam flux ratio between reactants can be varied, the preferred flux ratio being dependent on other growth parameters and on the nature of the nanowire or nanopyramid being grown.
  • the beam flux ratio between reactants can affect crystal structure of the nanowire.
  • growth of GaAs nanowires with a growth temperature of 540 °C, a Ga flux equivalent to a planar (layer by layer) growth rate of 0.6 ⁇ per hour, and a beam equivalent pressure (BEP) of 9 x 10 "6 Torr for As 4 produces wurtzite crystal structure.
  • BEP beam equivalent pressure
  • growth of GaAs nanowires at the same growth temperature, but with a Ga flux equivalent to a planar growth rate of 0.9 ⁇ per hour and a BEP of 4 x 10 "6 Torr for As 4 produces zinc blende crystal structure.
  • Nanowire or nanopyramid diameter can in some cases be varied by changing the growth parameters. For example, when growing self- catalyzed GaAs nanowires under conditions where the axial nanowire or nanopyramid growth rate is determined by the As 4 flux, the nanowire or nanopyramid diameter can be increased/decreased by increasing/decreasing the Ga:As 4 flux ratio. The skilled man is therefore able to manipulate the nanowire or nanopyramid in a number of ways.
  • RHEED reflection high-energy electron diffraction
  • the nanowires of the invention preferably grow as cubic (zinc blende) or hexagonal (wurtzite) structures.
  • the inventors have found that it is possible to change the crystal structure of the growing nanowire or nanopyramid by
  • MOVPE metal-organic chemical vapor deposition
  • radial and axial heterostructured nanowires can be grown using the MOVPE method.
  • this method favours the growth of radial heterostructured nanowires and micro wires, for example: n-doped GaN core with shell consisting of intrinsic GaN/InGaN multiple quantum wells (MQW), p-doped AlGaN electron blocking layer (EBL) and p-doped GaN shell.
  • MQW intrinsic GaN/InGaN multiple quantum wells
  • EBL p-doped AlGaN electron blocking layer
  • This method also allows the growth of axial heterostructured nanowires using techniques such as pulsed growth technique or continuous growth mode with modified growth parameters for e.g., lower V/III molar ratio and higher substrate temperature.
  • the reactor is evacuated after placing the sample, and is purged with N 2 to remove oxygen and water in the reactor. This is to avoid any damage to the graphitic substrate at the growth temperatures, and to avoid unwanted reactions of oxygen and water with the precursors.
  • the reactor pressure is set to be between 50 and 400 Torr.
  • the substrate is thermally cleaned under H 2 atmosphere at a substrate temperature of about 1200 °C.
  • a very thin buffer layer or nucleation islands is grown which consists of Al(In)GaN or A1N by introducing metal organic precursors and NH 3 .
  • the metal organic precursors can be either trimethylgallium (TMGa), or triethylgallium
  • TAGa for Ga
  • TMGa trimethylalumnium
  • TMAl triethylalumnium
  • TMIn trimethylindium
  • TEIn triethylindium
  • the metal precursors for dopants can be SiH 4 for silicon and bis(cyclopentadienyl)magnesium (Cp 2 Mg) or bis(methylcyclopentadienyl)magnesium ((MeCp) 2 Mg) for Mg.
  • the substrate temperature may be set in the range of 600 to 1200°C.
  • the flow rates of TMGa, TMAl and TMIn can be maintained between 5 and 100 seem.
  • the NH 3 flow rate can be varied between 5 and 550 seem.
  • TMGa/TMAl and NH 3 are supplied to the substrate surface for a period of time to initiate the formation of Al(In)GaN or A1N buffer layer or nucleation islands on the graphitic surface.
  • the growth parameters used for buffer layer or nucleation islands can strongly influence the density, polarity and alignment of the nanowires.
  • the substrate temperature can then be set to a temperature suitable for the growth of the nanowire or nanopyramid in question.
  • the growth temperature may be in the range 700 to 1200°C.
  • the temperature employed is, however, specific to the nature of the material in the nanowire.
  • GaN nanowires a preferred temperature is 800 to 1150°C, e.g. 900 to 1100 °C, such as 1100°C.
  • the range is slightly higher, for example 900 to 1400°C, such as 1050 to 1250°C, e.g. 1250°C.
  • the nanowires or nanopyramids of the invention preferably grow epitaxially. They attach to the underlying substrate through covalent, ionic or quasi van der
  • the substrate can be doped to match the major carriers of grown nanowires or nanopyramids.
  • the bottom contact is preferably ohmic.
  • inventive compositions comprise a plurality of nanowires or nanopyramids.
  • the nanowires or nanopyramids grow about parallel to each other. It is preferred therefore if at least 90%, e.g. at least 95%, preferably substantially all nanowires or nanopyramids grow in the same direction from the same plane of the growing surface.
  • the grown nanowires or nanopyramids are substantially parallel.
  • the nanowires or nanopyramids grow substantially perpendicular to the growing surface.
  • nanowires or nanopyramids of the invention can contain a p-n or p-i-n junction, e.g. to enable their use in LEDs.
  • Nanowires or nanopyramids of the invention are therefore provided with an undoped intrinsic semiconductor region between a p-type semiconductor and an n-type semiconductor region. All of or sections of the p-type and n-type regions are typically heavily doped because they are used for ohmic contacts.
  • the nanowires or nanopyramids are doped. Doping typically involves the introduction of impurity ions into the nanowire, e.g. during MBE or MOVPE growth. The doping level can be controlled from
  • the nanowires or nanopyramids can be p-doped or n-doped as desired.
  • Doped semiconductors are extrinsic semiconductors.
  • the n(p)-type semiconductors have a larger electron (hole) concentration than hole (electron) concentration by doping an intrinsic semiconductor with donor (acceptor) impurities.
  • Suitable donor (acceptors) for III-V compounds can be Te (Mg, Be and Zn).
  • Dopants can be introduced during the growth process or by ion implantation of the nanowires or nanopyramids after their formation.
  • the nanowires or nanopyramids of the invention comprise Al.
  • the use of Al is advantageous as high Al content leads to high band gaps, enabling UV-C LED emission from the active layer(s) of nanowires or nanopyramids and/or avoiding absorption of the emitted light in the p-region and/or n-region layers. Where the band gap is high, it is less likely that UV light is absorbed by this part of the nanowires or nanopyramids.
  • the use therefore of A1N or AlGaN in nanowires or nanopyramids is preferred.
  • nanowires or nanopyramids comprise A1N or AlGaN
  • achieving high electrical conductivity by introducing p-type dopants is a challenge.
  • SPSL short period superlattice
  • a superlattice structure consisting of alternating layers with different Al content instead of a homogeneous AlGaN layer with higher Al composition.
  • the low ionization energy of acceptors in layers with lower Al composition leads to improved hole injection efficiency without compromising on the barrier height in the p-region layer. This effect is additionally enhanced by the polarization fields at the interfaces.
  • the SPSL can be followed with a highly p- doped GaN:Mg layer for better hole injection.
  • the inventors propose to introduce a p-type doped AL-Ga;_ JNi/AlyGay-yN short period superlattice (i.e. alternating thin layers and AlyGay-yN) into the nano wires or nanopyramid structure, where the Al mole fraction x is less than y, instead of a p-type doped Al z Ga;_ z N alloy where x ⁇ z ⁇ y. It is appreciated that x could be as low as 0 (i.e. GaN) and y could be as high as 1 (i.e. A1N).
  • the superlattice period should preferably be 5 nm or less, such as 2 nm, in which case the superlattice will act as a single Al z Ga;_ z N alloy (with z being a layer thickness weighted average of x and y) but with a higher electrical conductivity than that of the Al z Ga;_ z N alloy, due to the higher p-type doping efficiency for the lower Al content layers.
  • the p-type dopant is an alkali earth metal such as Mg or Be.
  • nanowire/nanopyramid follows similar principles. Instead of a superlattice containing thin AlGaN layers with low or no Al content, a nanostructure can be designed containing a gradient of Al content (mole fraction) in the growth direction of the AlGaN within the nanowires or nanopyramids. Thus, as the nanowires or nanopyramids grow, the Al content is reduced/increased and then increased/reduced again to create an Al content gradient within the nanowires or nanopyramids.
  • the layers are graded either from GaN to A1N or A1N to GaN.
  • the graded region from GaN to A1N and A1N to GaN may lead to n-type and p-type conduction, respectively. This can happen due to the presence of dipoles with different magnitude compared to its neighbouring dipoles.
  • the GaN to A1N and A1N to GaN graded regions can be additionally doped with n-type dopant and p-type dopant respectively.
  • p-type doping is used in AlGaN nanowires using Be as a dopant.
  • Be as a dopant.
  • a GaN nanowire/nanopyramid and increase Al and decrease Ga content gradually to form A1N, perhaps over a growth thickness of 100 nm.
  • This graded region could act as a p- or n-type region, depending on the crystal plane, polarity and whether the Al content is decreasing or increasing in the graded region, respectively.
  • the opposite process is effected to produce GaN once more to create an n- or p-type region (opposite to that previously prepared).
  • graded regions could be additionally doped with n-type dopants such as Si and p-type dopants such as Mg or Be to obtain n- or p-type regions with high charge carrier density, respectively.
  • n-type dopants such as Si
  • p-type dopants such as Mg or Be
  • the crystal planes and polarity is governed by the type of nanowire/nanopyramid as is known in the art.
  • the nanowires or nanopyramids of the invention comprise Al, Ga and N atoms wherein during the growth of the nanowires or nanopyramids the concentration of Al is varied to create an Al concentration gradient within the nanowires or nanopyramids.
  • a tunnel junction is a barrier, such as a thin layer, between two electrically conducting materials.
  • the barrier functions as an ohmic electrical contact in the middle of a semiconductor device.
  • a thin electron blocking layer is inserted immediately after the active region, which is followed by a p-type doped AlGaN layer with Al content higher than the Al content used in the active layers.
  • the p-type doped layer is followed by a highly p-type doped AlGaN layer and a very thin tunnel junction layer followed by an n-type doped AlGaN layer.
  • the tunnel junction layer is chosen such that the electrons tunnel from the valence band in p-AlGaN to the conduction band in the n- AlGaN, creating holes that are injected into the p- AlGaN layer.
  • the nanowire or nanopyramid comprises two regions of doped GaN (one p- and one n-doped region) separated by an Al layer, such as a very thin Al layer.
  • the Al layer might be a few nm thick such as 1 to 10 nm in thickness. It is appreciated that there are other optional materials that can serve as a tunnel junction which includes highly doped InGaN layers. It is particularly surprising that doped GaN layers can be grown on the Al layer.
  • the invention provides a nanowire or nanopyramid having a p-type doped (Al)GaN region and an n-type doped (Al)GaN region separated by an Al layer.
  • the nanowires or nanopyramids of the invention can be grown to have a heterostructured form radially or axially.
  • p-n junction can be axially formed by growing a p-type doped core first, and then continue with an n-doped core (or vice versa).
  • heterostructured nanowire, p-n junction can be radially formed by growing the p- doped nanowire or nanopyramid core first, and then the n-doped semiconducting shell is grown (or vice versa) - a core shell nanowire.
  • An intrinsic shell can be grown between doped regions to obtain a radially heterostructured nanowire or nanopyramid with p-i-n junction.
  • the nanowires or nanopyramids are grown axially and are therefore formed from a first section and a second section.
  • the two sections are doped differently to generate a p-n junction or p-i-n junction. It does not matter whether the top or bottom section of the nanowire or nanopyramid is the p-doped or n-doped section.
  • nanowires have been grown on a substrate in the presence of a catalyst, it is envisaged that some of the nanowires will have a catalyst deposit on top of nanowire. Ideally, the majority of the nanowires will have such a deposit, preferably substantially all the nanowires will comprise this deposit.
  • the top of the nanowires or nanopyramids needs to comprise a top contact.
  • a top contact is formed using another graphitic layer.
  • the invention then involves placing a graphitic layer on top of the formed nanowires or nanopyramids to make a top contact. It is preferred that the graphitic top contact layer is substantially parallel with the substrate layer. It will also be appreciated that the area of the graphitic layer does not need to be the same as the area of the substrate. It may be that a number of graphitic layers are required to form a top contact with a substrate with an array of nanowires or nanopyramids.
  • the graphitic layers used can be the same as those described in detail above in connection with the substrate.
  • the top contact is graphitic, more especially it is graphene.
  • This graphene top contact should contain no more than 10 layers of graphene or its derivatives, preferably no more than 5 layers (which is called as a few-layered graphene). Especially preferably, it is a one-atom-thick planar sheet of graphene.
  • the crystalline or "flake” form of graphite consists of many graphene sheets stacked together (i.e. more than 10 sheets). It is preferred if the top contact is 20 nm in thickness or less. Even more preferably, the graphitic top contact may be 5 nm or less in thickness.
  • the inventors have realized that the growing of semiconductor nanowires can involve metal catalysis.
  • the metal catalysts such as Au, Ga, or In are preferably used as seeds for nanowire or nanopyramid growth and they remain as a form of nanoparticles on top of nanowires after completion of the nanowire or nanopyramid growth.
  • These catalyst deposits can be used as an intermediate material between metallic graphene and
  • the Schottky contact formed at the interface between metallic graphitic top contact and the semiconductor nanowire or nanopyramid can be avoided and ohmic contact can be established.
  • top contact to the formed nanowires can be achieved by any convenient method. Methods akin to those mentioned previously for transferring graphitic layers to substrate carriers may be used.
  • the graphitic layers from Kish graphite, highly ordered pyrolytic graphite (HOPG), or CVD may be exfoliated by mechanical or chemical methods. Then they can be transferred into etching solutions such as HF or acid solutions to remove Cu (Ni, Pt, etc.) (especially for CVD grown graphitic layers) and any contaminants from the exfoliation process.
  • the etching solution can be further exchanged into other solutions such as deionised water to clean the graphitic layers.
  • the graphitic layers can then be easily transferred onto the formed nanowires as the top contact. Again e-beam resist or photoresist may be used to support the thin graphitic layers during the exfoliation and transfer processes, which can be removed easily after deposition.
  • the graphitic layers are dried completely after etching and rinsing, before they are transferred to the top of the nanowire or nanopyramid arrays.
  • a mild pressure and heat can be applied during this "dry" transfer.
  • the graphitic layers can be transferred on top of the nanowire or nanopyramid arrays, together with a solution (e.g. deionised water). As the solution dries off, the graphitic layers naturally form a close contact to underlying nanowires. In this "wet" transfer method, the surface tension of the solution during the drying process might bend or knock out the nanowire or nanopyramid arrays. To prevent this, where this wet method is used, more robust nanowires are preferably employed. Nanowires having a diameter of > 80 nm might be suitable.
  • hole patterned substrates which support the perpendicular nanowire or nanopyramid structure could be used.
  • the fill-in material needs to be transparent to the emitted or detected light.
  • the top contact graphitic layer is preferably transparent, conductive and flexible.
  • a post-annealing process may be used. After the deposition of the graphitic top contact, the sample can be annealed in an inert atmosphere, e.g. of argon, or vacuum. Temperatures can be up to 600°C. Annealing times can be up to 10 min.
  • doping of the graphitic top contact can be utilized.
  • the major carrier of the graphitic top contact can be controlled as either holes or electrons by doping. It is preferable to have the same doping type in the graphitic top contact and in the semiconducting nanowires, especially at the region below the metal catalytic particles, which would give a better ohmic behaviour after the post-annealing process. For example, for a core-shell nanowire or nanopyramid with p-doping in the shell, p-doping of the top graphitic layers matches the carrier type across the metal particles at the top of the nanowire or nanopyramid shell.
  • top graphitic layer and the substrate can be doped.
  • the substrate and/or the graphitic layer is doped by a chemical method which involves with an adsorption of organic or inorganic molecules such as metal chlorides (FeCl 3 , AuCl 3 or GaCl 3 ), N0 2 , HN0 3 , aromatic molecules or chemical solutions such as ammonia.
  • organic or inorganic molecules such as metal chlorides (FeCl 3 , AuCl 3 or GaCl 3 ), N0 2 , HN0 3 , aromatic molecules or chemical solutions such as ammonia.
  • the surface of substrate and/or the graphitic layer could also be doped by a substitutional doping method during its growth with incorporation of dopants such as B, N, S, or Si.
  • Semiconductor nanowires or nanopyramids have wide ranging utility. They are semiconductors so can be expected to offer applications in any field where semiconductor technology is useful. They are primarily of use in integrated nanoelectronics and nano -opto electronic applications. An ideal device for their deployment might be a solar cell in particular. One possible device is a nanowire or nanopyramid solar cell sandwiched between two graphene layers as the two terminals.
  • Such a solar cell has the potential to be efficient, cheap and flexible at the same time. This is a rapidly developing field and further applications on these valuable materials will be found in the next years.
  • the same concept can be used to also fabricate other opto-electronic devices such as light-emitting diodes (LEDs), photodetectors, waveguides and lasers.
  • devices of the invention are provided with electrodes to enable charge to be passed into the device.
  • Figure 1(a) shows a schematic representation of deposition of buffer layer on graphitic substrate, followed by the nanowire growth.
  • Figure 1(b) shows a schematic representation of deposition of nucleation islands on graphitic substrate, followed by the nanowire growth.
  • Figure 2 shows representative results of the formation of nucleation island and nanowire growth scheme, (a) SEM image of AlGaN nucleation islands grown on graphene by MOVPE. (b) SEM image of GaN nano wires grown on the AlGaN nucleation islands on graphene by MOVPE. Inset: SEM image of GaN growth without AlGaN nucleation islands on graphene, where no growth of perpendicular GaN nanowires can be seen.
  • Figure 3(a) is a cross-sectional high-resolution scanning transmission electron microscope (STEM) image of a GaN nanowire grown on graphene using AlGaN nucleation islands.
  • Figure 3(b) is a high-angle annular dark- fie Id STEM image of the same nanowire in (a), showing the AlGaN nucleation island.
  • Figure 4a is a SEM image of (Al)GaN nanopyramids of the invention grown in a regular array. After growing the AlGaN nucleation islands, AlGaN with 3% Al in gas phase was grown for 150 s.
  • Figure 4b is a closer image of said nanopyramids.
  • Figure 5 (a) Schematic diagram showing the growth of nanowires on graphite flake and the top and bottom contacts to the nanowires. Tilted view SEM image (b) and high-resolution SEM image (c) of selectively grown GaN nanowires on multi-layer graphene flakes by MBE.
  • Figure 6 shows an SEM image of self-catalyzed GaAsSb nanowires grown by MBE using AlAsSb nanoscale islands for enhanced nucleation on pristine graphitic substrate.
  • Inset Magnified view of the perpendicular GaAsSb nanowires.
  • Figure 7 shows atomic force microscopy (AFM) topography image after the treatment of graphite with (a) UV-ozone and (b) UV-ozone and H 2 annealing in Ar atmosphere.
  • AFM atomic force microscopy
  • Figure 8(a) shows the AFM height profile along the solid line in Figure 6(a) of the graphite surface after the treatment with UV-ozone.
  • Figure 8(b) shows the AFM height profile along the dashed line in Figure 6(b) of the graphite surface after the UV-ozone treatment and the following H 2 annealing in Ar atmosphere, showing the formation of atomic steps and ledges. (Nanowires or nanopyramids are then grown on the treated graphitic substrate.)
  • Figure 9(a) shows an SEM image of GaAsSb nanowires grown on untreated pristine graphitic surface.
  • Figure 9(b) shows an SEM image of GaAsSb nanowires grown on UV-ozone treated and H 2 annealed graphitic surface. Improved density of perpendicular nanowires can be seen in (b) as compared to (a).
  • Figure 10 shows the main process steps of aluminium- induced crystallization (MIC) of silicon on graphene layer 1, where amorphous silicon (a-Si) layer 3 diffuses through an aluminium metal layer 2 by thermal activation. At the graphene- Al interface the silicon rearranges into a polycrystalline structure (p-Si) with [1 11]- orientation. The aluminium metal layer and the oxide layer above the p-Si structure may be etched using HC1 and HF, respectively. (Nanowires or nanopyramids are then grown on the MIC silicon on graphene.)
  • Figure 11 shows an SEM image of self-catalyzed GaAs nanowires grown by MBE on amorphous (Si0 2 ) substrate covered with MIC silicon.
  • the reactor was evacuated and purged with N 2 to remove oxygen and water in the reactor.
  • the reactor pressure was set to 75 Torr and H 2 was used as the carrier gas for the growth.
  • the substrate was thermally cleaned under H 2 atmosphere at a substrate temperature of -1200 °C for 5 min.
  • a nitridation step was carried out using NH 3 flow of 600 seem for 10 min.
  • TMGa and TMAl was introduced for 40 s with a flow of 44.8 and 26.3 ⁇ mol/min, respectively, to grow AlGaN nucleation islands, followed by a 2 min nitridation step.
  • the substrate temperature was lowered to -1150 °C and the NH 3 flow was set to 25 seem.
  • Si-doped GaN nanowire growth was carried out for -3.5 min by introducing TMGa and Silane with a flow of 44.8 and 0.03 ⁇ mol/min, respectively. After the growth, the sample was cooled down under NH 3 flow of 25 seem until the temperature dropped below 500 °C.
  • multi-layer graphene was mechanically exfoliated from Kish graphite flakes and then indium-bonded to a Si0 2 /Si supporting substrate.
  • a mask material such as A1 2 0 3 and Si0 2 can be optionally deposited on the graphite flake.
  • a big hole of 10 ⁇ in diameter is etched in the mask material using photolithography such that the graphite surface is exposed in the hole.
  • several periodically spaced small holes of diameter -100 nm can be etched using e- beam lithography, such that the nanowires selectively grow on the graphitic surface exposed in the hole.
  • the nitrogen plasma treatment and the nanowire growth were carried out in a Veeco Gen 930 MBE system equipped with a nitrogen plasma source, a Ga dual filament cell, and an Al double-crucible cell.
  • the above samples are then loaded into the MBE system for sample outgassing and nanowire growth.
  • the samples are annealed at a substrate
  • the substrate temperature is then increased to a temperature suitable for GaN nanowire growth: i.e. typically 755 °C.
  • the temperatures of the Ga and Al effusion cell is preset to yield nominal planar growth rate of 0.3 and 0.2 ⁇ per hour, respectively.
  • the nitrogen plasma is generated using a RF generator power of 450 W and nitrogen gas flow of 2.8 seem.
  • the gate valve and the shutter in front of the nitrogen source was opened for 1 min, such that the nitrogen plasma is directed on to the sample.
  • the sample can then either be subjected to the nanowire growth by MBE or taken out of the MBE growth chamber for the nanowire or nanopyramid growth by MOCVD.
  • an Al flux was supplied for 6 seconds or longer and then an Al flux and a nitrogen plasma was supplied for 1 minute or longer.
  • the opening of the shutter in front of the Ga and nitrogen source to supply Ga flux and nitrogen plasma simultaneously, to initiate the growth of intrinsic (intentionally undoped) GaN nanowires.
  • Si dopant was supplied to obtain n-type GaN nanowires and either Be or Mg dopant was supplied to obtain p-type GaN nanowires.
  • all the shutters are closed and simultaneously the substrate temperate is ramped down.
  • Nanowires are grown in a Varian Gen II Modular MBE system equipped with a Ga dual filament cell, an Al double-crucible cell, an As valved cracker cell, and an Sb valved cracker cell.
  • the cracker cells allow to fix the proportion of monomers, dimers and tetramers.
  • the major species of arsenic and antimony are As 2 and Sb 2 , respectively.
  • Growth of NWs is performed either on a Kish graphite flake or on a graphene film grown on SiC substrates by using a high-temperature sublimation technique.
  • the graphene film samples are purchased from external supplier.
  • the Kish graphite samples are cleaned by isopropanol followed by a blow dry with nitrogen, then indium-bonded to a silicon wafer and finally cleaved to provide a fresh graphitic surface for growth of NWs.
  • the graphene/SiC substrates are blow dried with nitrogen, and then indium-bonded to a silicon wafer.
  • the samples are then loaded into the MBE system for sample outgassing and nanowire growth.
  • the samples are annealed at a substrate temperature of 550 °C for a duration of 30 min to get rid of any oxide residues on the substrate.
  • the substrate temperature is then increased to a temperature suitable for GaAs or GaAsSb nanowire growth: i.e. 630 °C.
  • the temperatures of the Al and Ga effusion cells are preset to yield nominal planar growth rates of 0.1 ⁇ per hour and 0.7 ⁇ per hour, respectively.
  • an As 2 flux of 2.5 x 10 "6 Torr is used, whereas the Sb 2 flux is set to a value in the range 0 - 1 x 10 "6 Torr (dependent on the intended GaAsSb composition), for example 6x 10 "7 Torr.
  • the Al flux is first supplied to the surface during a time interval of typically 1 s or longer, while the shutters/valves for the other sources are closed.
  • the Al shutter is then closed and As and/or Sb flux are supplied to the surface for a time interval of typically 60 s to form AlAs(Sb) nanoscale islands on the graphitic surface.
  • the group V shutters and valves are then closed and the Ga shutter opened, typically for 5 s, to supply Ga flux to the surface to initiate the formation of Ga droplets at the nanoscale islands.
  • the relevant group V shutters and valves are then opened again to initiate the growth of nanowires.
  • Kish graphite flakes were used as the graphitic substrates.
  • the Kish graphite samples are cleaned by isopropanol followed by a blow dry with nitrogen, then indium-bonded to a silicon wafer and finally cleaved to provide a fresh graphitic surface for growth of nanowires.
  • the substrates were treated in UV-ozone at -150 °C for 6 min, followed by annealing in H 2 at -300 °C for 45 min.
  • Nanowires are grown in the same MBE system as described in Example 3.
  • arsenic and antimony are As 2 and Sb 2 , respectively.
  • the samples are loaded into the MBE system and outgassed at -550 °C for a duration of 30 min to get rid of any oxide residues on the substrate.
  • the substrate temperature is then increased to a temperature suitable for GaAs or GaAsSb nanowire growth: i.e. 630 °C.
  • the temperatures of the Ga effusion cell is preset to yield nominal planar growth rate of 0.7 ⁇ per hour.
  • Ga flux was supplied for 10 s at a substrate temperature of -630 °C. After that the temperature is reduced to -250 °C and an Sb 2 flux of 8x 10 "7 Torr and As 2 flux of 2.5x 10 "6 Torr are subsequently supplied for 50 s and 40 s, respectively. Then the substrate temperature is again increased to -630 °C.
  • Ga flux was supplied for 10 min together with an As 2 flux of 2.5 x 10 "6 Torr, whereas the Sb 2 flux is set to a value in the range 0 - l x lO "6 Torr (dependent on the intended GaAsSb composition), for example 8 ⁇ 10 "7 Torr.
  • the MIC poly-Si(l 11) on graphene samples were of commercial chemical vapor deposition (CVD) grown monolayer graphene transferred onto Si(001).
  • CVD chemical vapor deposition
  • 50 nm Al was deposited by e-beam evaporation at a rate of 1 A/s and a pressure of ⁇ 10 Torr.
  • the samples were oxidized for 24 h in an IS05 cleanroom atmosphere before depositing 50 nm amorphous Si (a-Si) by e-beam evaporation at a rate of 1 A/s and a pressure of ⁇ 10 8 Torr. All depositions were done at room temperature.
  • the samples were annealed for 15 h at 500 °C in a nitrogen gas. After the layer exchange by annealing, the top layer of Al was removed by etching in a phosphoric acid mixture.

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Abstract

La présente invention concerne un procédé de croissance de nanofils ou de nanopyramides consistant à (I) prendre un substrat graphitique et à déposer AlGaN, InGaN, AlN ou AlGa(In)N sur ledit substrat graphitique à une température élevée pour former une couche tampon ou des îlots de nucléation à l'échelle nanométrique desdits composés; (II) à faire croître une pluralité de nanofils ou de nanopyramides de groupes III-V semi-conducteurs, de préférence des nanofils ou des nanopyramides de nitrure III, sur ladite couche tampon ou lesdits îlots de nucléation sur le substrat graphitique, de préférence par MOVPE ou MBE.
EP16754215.8A 2015-07-31 2016-08-01 Procédés de croissance de nanofils ou de nanopyramides sur des substrats graphitiques Pending EP3329509A1 (fr)

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